KR20120119998A - vel Diblock Copolymer, Preparation Method Thereof, And Method Of Forming Nano Pattern Using The Same - Google Patents

Abstract

PURPOSE: A diblock copolymer is provided to facilitate the formation of micro nanopatterns, and to be used for manufacturing nano bio sensors or electronic element comprising nanopatterns, etc. CONSTITUTION: A diblock copolymer comprises a hard segment comprising one or more kinds of a repeating unit indicated in chemical formula 1 and a soft segment comprising one or more kinds of (meth)acrylate-based repeating units indicated in chemical formula 2. In chemical formula 1, n is an integer from 5-600, R is hydrogen or methyl, R' is X, -Y-NHC(O)-X, -X-Y-C(O)NH-X, -X-Y-C(O)NH-Y-C(O)NH-X or -X-Y-C(O)NH-Y-C(O)NH-Y-C(O)NH-X, X is -Z-R", Y is C1-10 alkylene, Z is C6-20 arylene, R" is C10-20 linear or branched hydrocarbon, or C10-20 linear or branched perfluorohydrocarbon. In chemical formula 2, m is an integer from 30-1000, R1 is a hydrogen or methyl, and R2 is C1-20.

Description

Novel diblock copolymer, preparation method thereof and nano pattern formation method using the same {vel Diblock Copolymer, Preparation Method Thereof, And Method Of Forming Nano Pattern Using The Same}

The present invention relates to a novel diblock copolymer, a method for preparing the same, and a method for forming a nanopattern using the same. More specifically, the present invention facilitates the formation of finer nano-patterns, diblock copolymers that can be used in the manufacture of electronic devices or nano-biosensors including nano-patterns, methods for their preparation and methods of forming nano-patterns using the same It is about.

 As nanotechnology advances rapidly, not only the demand for nanoscale materials increases, but also the size of electronic devices becomes smaller. Accordingly, the photolithography method, a top-down approach used to fabricate a conventional silicon device, has reached a technical limit. That is, currently used photolithography technology for manufacturing silicon semiconductor has many advantages in terms of process optimization and application, but it is difficult to manufacture printed circuits of 30 nm or less due to technical limitations such as light dispersion and wavelength of light source. It is known. In addition, research on electron beam lithography or extreme ultraviolet (EUV) lithography is also in progress. However, in the case of the former, it is difficult to simultaneously form a two-dimensional pattern, and in the latter, it is difficult to control the lifetime of the optical device or the light absorbed by the photoresist because the latter must use a very high light energy.

Therefore, in order to develop the next-generation semiconductor, it is necessary to overcome the problems of the existing photolithography technology, and at the same time, reduce the production cost and simplify the process. Recently, self-assembly of block copolymers has been studied as a method to satisfy these conditions. Above all, unlike the conventional method, the method of forming a pattern using the nanostructure of the block copolymer has an advantage of simultaneously forming a two-dimensional pattern. In particular, since the formation of the nanostructure is caused by a simple microphase separation between the chains of the block copolymer, it is possible to lower the process cost according to the pattern formation.

A block copolymer is a polymer in which polymer blocks having different chemical structures are connected through covalent bonds, and spheres are formed according to the composition of the blocks, the length of the chain, and the fluorescence-Huggins parameter. It is possible to form nanostructures ranging from basic structures such as cylinders and lamellaes to complex three-dimensional structures such as gyroid and hexagonal perforated lamellae (HPL) structures. In addition, the size of the nanostructure can be arbitrarily adjusted from 5 to 50 nm depending on the chemical structure of the block copolymer, the composition ratio of the block, or the molecular weight. Lithography using a block copolymer (pattern forming method) refers to a nanopattern by transferring a nanostructure present in a thin film of a block copolymer onto a substrate. Compared with the photolithography used in the current semiconductor manufacturing process, the cost is significantly lower and the manufacturing process can be very simple.

On the other hand, as the polymer synthesis technology is greatly developed, researches on chemical physical factors on the synthesis and nanostructure of various block copolymers have been extensively performed. In particular, research on the control of nanostructures using PS-PMMA (polystyrene-polymethacrylate) based amorphous block copolymer has been the most intensively conducted. That is, by adjusting the morphology of the PS-PMMA block copolymer by the microphase separation phenomenon, the cylindrical nanostructures arranged in a hexagonal shape are easily formed. However, since the cylindrical nanostructures arranged in the hexagonal shape are not suitable for use in the microcircuit printing process of the semiconductor industry, the manufacturing time of related electronic devices is long and energy is consumed.

Therefore, from the economical point of view and the design and software of the semiconductor circuit, the cylindrical nanostructures arranged in a square shape are much more advantageous for manufacturing electronic devices than the cylindrical nanostructures arranged in a hexagonal shape. For this reason, studies have been actively conducted to form cylindrical nanostructures arranged in squares using self-assembly or microphase separation of block copolymers. For example, a study has been reported that a PS-PMMA diblock copolymer is coated on a substrate having a rectangular chemical pattern engraved thereon and then forced to form a rectangular nanostructure. However, if the period of the chemical pattern and the period of the block copolymer nanostructure do not coincide, there is a problem in that the nanostructures arranged in a square are not formed.

On the other hand, when using the A-B-C type triblock copolymer having three blocks instead of the above-described diblock copolymer, it has been reported that the nanostructures arranged in a square shape in a narrow area are formed. In addition, in the case of the triblock copolymer having a core-shell spherical nanostructure, it has been reported that some square array nanostructures are formed only at the top layer depending on the film thickness. It has been suggested to apply to the next generation nanopatterning technology by implementing the cylindrical nanostructure of the square array that could not be obtained in the diblock copolymer by introducing into the copolymer.

However, in view of all the previous studies mentioned above, in order to form cylindrical nanostructures arranged in a square shape suitable for semiconductor circuit design, micrometer level together with a diblock copolymer which is a substrate for forming nanostructures, Using a photomask having a structural or chemical pattern separately, preparing and using an ABC-type triblock copolymer which is difficult to synthesize due to its complicated molecular structure, or an additive or intermolecular hydrogen bond that induces a nanostructure It was necessary to use the mixture further. For this reason, the situation is still insufficient to be applied to the next generation nanopatterning technology, which is too complicated or economically large. In addition, none of the existing PS-PMMA diblock copolymers that have been intensively studied, but also any kind of diblock copolymers, could not directly form cylindrical nanostructures arranged in a square shape without auxiliary or additives engraved with nanostructures. .

In other words, all of the prior arts known so far cannot form cylindrical nanostructures arranged in a square shape, or require complicated processing such as a separate use of a photomask or complicated synthesis of the block copolymer itself. It was. For this reason, no known method of forming a pattern using any block copolymer has been able to easily form a cylindrical nanostructure arranged in a square shape, so that it cannot be suitably applied to the design and mass production process of a semiconductor circuit.

The present invention relates to a diblock copolymer and a method for preparing the same, which makes it possible to easily form a finer nano pattern, for example, a cylindrical nanostructure arranged in a square shape.

In addition, the present invention relates to a polymer thin film and a method for manufacturing the same, including the diblock copolymer, which can be suitably used for the production of electronic devices or nano biosensors including finer nano patterns.

The present invention also relates to a method of forming a nanopattern using the polymer thin film.

The present invention provides a diblock copolymer comprising a hard segment including at least one repeating unit of Formula 1 and a soft segment containing at least one (meth) acrylate-based repeating unit of Formula 2 below:

[Formula 1]

[Formula 2]

,

,

또는

이고, X는 -Z-R＂이고, Y는 탄소수 1 내지 10의 알킬렌이고, Z는 탄소수 6 내지 20의 아릴렌이고, R＂은 탄소수 10 내지 20의 선형 또는 분지형 탄화수소, 또는 탄소수 10 내지 20의 선형 또는 분지형 퍼플루오로하이드로카본(perfluorohydrocarbon)이고, In Formula 1, n is an integer of 5 to 600, R is hydrogen or methyl, R 'is X,

,

,

or

X is -ZR ', Y is alkylene having 1 to 10 carbon atoms, Z is arylene having 6 to 20 carbon atoms, and R' is a linear or branched hydrocarbon having 10 to 20 carbon atoms, or 10 to 20 carbon atoms. Linear or branched perfluorohydrocarbons,

In Formula 2, m is an integer of 30 to 1000, R ₁ is hydrogen or methyl, R ₂ is alkyl having 1 to 20 carbon atoms.

In addition, the present invention comprises the steps of RAFT polymerization of a reactant comprising at least one (meth) acrylate monomer of formula (3) in the presence of a radical initiator and a reversible addition fragmentation chain transfer (RAFT) reagent; And RAFT polymerizing a reactant comprising at least one monomer of Formula 4 in the presence of the polymerization product.

(3)

[Formula 4]

In Formulas 3 and 4, R ₁ , R ₂ , R and R 'are as defined in Formulas 1 and 2.

The present invention also provides a polymer thin film comprising the diblock copolymer, wherein the remaining segments are regularly arranged in the form of a cylinder or a sphere on any one of the hard segment or the soft segment. Such a polymer thin film, when viewed on any one plane of the thin film, the cylinder shape may be a regular arrangement in a lamellar, square or hexagonal shape.

In addition, the present invention comprises the steps of applying a solution of the diblock copolymer on a substrate to form a thin film; And solvent aging the applied thin film in a mixed solvent of a non-polar solvent and a polar solvent, or thermally treating the hard segment at the melting point of the hard segment and the glass transition temperature of the soft segment.

The present invention also includes the steps of forming a polymer thin film on the substrate on which the pattern target film is formed; Irradiating ultraviolet light to the polymer thin film to remove the soft segment; And a reactive ion etching of the pattern target layer using the polymer thin film from which the soft segment has been removed as a mask.

Hereinafter, a diblock copolymer according to a specific embodiment of the present invention, a method for manufacturing the same, a polymer thin film including the same, a method for preparing the same, and a nano pattern forming method using the polymer thin film will be described in detail.

According to one embodiment of the invention, the diblock copolymer comprising a hard segment containing at least one repeating unit of formula 1 and a soft segment containing at least one (meth) acrylate-based repeating unit of formula (2) Is provided:

[Formula 1]

[Formula 2]

,

,

또는

이고, X는 -Z-R＂이고, Y는 탄소수 1 내지 10의 알킬렌이고, Z는 탄소수 6 내지 20의 아릴렌이고, R＂은 탄소수 10 내지 20의 선형 또는 분지형 탄화수소, 또는 탄소수 10 내지 20의 선형 또는 분지형 퍼플루오로하이드로카본이고, 상기 화학식 2에서, m은 30 내지 1000의 정수이고, R₁은 수소 또는 메틸이고, R₂는 탄소수 1 내지 20의 알킬이다. In Formula 1, n is an integer of 5 to 600, R is hydrogen or methyl, R 'is X,

,

,

or

X is -ZR ', Y is alkylene having 1 to 10 carbon atoms, Z is arylene having 6 to 20 carbon atoms, and R' is a linear or branched hydrocarbon having 10 to 20 carbon atoms, or 10 to 20 carbon atoms. Linear or branched perfluorohydrocarbon, wherein in Formula 2, m is an integer of 30 to 1000, R ₁ is hydrogen or methyl, R ₂ is alkyl having 1 to 20 carbon atoms.

MEANS TO SOLVE THE PROBLEM The present inventors are novel by the method of sequentially polymerizing a predetermined (meth) acrylate type monomer and an acrylamide type monomer (The monomer of Formula 3 and 4 mentioned below; same as below.) Through RAFT polymerization method known as a living radical polymerization method. The diblock copolymer of was synthesized and its properties were found. In particular, when the diblock copolymer is treated by a solvent aging method or a heat treatment method described later, a hard segment including the acrylamide repeating unit of Formula 1 or a soft containing the (meth) acrylate repeating unit of Formula 2 On one of the segments, it was confirmed that a polymer thin film having a nanostructure (nano pattern) in which the remaining segments were regularly arranged in a cylinder form or the like could be produced. In addition, the diblock copolymer and the polymer thin film may have a nano structure in which the cylinder form is regularly arranged in a square shape or the like by adjusting the treatment conditions of the solvent aging method or the heat treatment method.

Therefore, using the diblock copolymer, not only enables the formation of fine nanopatterns compared to photolithography that has been applied until now, but also, in particular, the nanopatterns may include a cylindrical pattern that is regularly arranged in a square shape or the like. Therefore, it is suitable for the circuit design of semiconductor devices and can be applied very well to the formation of fine patterns of devices. In addition, the above-described nanopattern can be formed only by controlling the morphology structure of the diblock copolymer itself without the application of a complex triblock copolymer or a metal mold aid such as a separate photomask in which the nanostructure is pre-processed. Therefore, it was confirmed that the diblock copolymer can be suitably applied to a fine pattern forming process of an electronic device including a next-generation semiconductor device, or to manufacturing a nano biosensor.

As such, it is possible to form the above-described regular nanostructures or nanopatterns using the diblock copolymers in the self-assembly behavior of the acrylamide-based polymer blocks of the general formula (1) constituting the hard segment and the microphase separation phenomenon with the soft segment. It seems to be caused by. This technical cause will be described in more detail as follows.

The polymer block constituting the hard segment (ie, the repeating unit of Formula 1) may be obtained by RAFT polymerization of a predetermined acrylamide monomer described later. However, such acrylamide-based monomers may cause hydrogen bonds in intramolecular or intermolecular interactions with nonpolar aliphatic hydrocarbons capable of self-assembly (more than 10 carbon atoms), arylene groups causing interaction of π-π orbitals Amide groups have a chemical structure introduced. Through the self-assembly behavior of aliphatic long-chain hydrocarbons, the π-π interaction of arylene groups, and the intermolecular hydrogen bonding of amide groups, the monomers have a regular monoclinic crystal structure in the solid state. structure, for example, monoclinic single crystal.

Therefore, when RAFT polymerization is performed on such monomers, living radical polymerization occurs in a state in which the monomer molecules are well aligned, and thus, each monomer molecule may be regularly arranged in the polymer chain. More specifically, through the polymerization reaction, well-oriented monomer molecules may combine to form one polymer chain (for example, one polymer building block), and the polymer building blocks may be assembled to form a regularly arranged polymer. Can be formed. Therefore, due to the orderly arrangement of polymer building blocks in such polymers, the polymer blocks of the hard segment (ie, repeating units of Formula 1) are characterized by self-assembly properties that define a number of spaces of uniform size after polymerization and It may indicate crystallinity.

However, the diblock copolymer is prepared by RAFT polymerization of the acrylamide monomer in a state in which a polymer block forming a soft segment is formed by RAFT polymerization of the (meth) acrylate monomer. Accordingly, when the RAFT polymerization of the acrylamide-based monomer is performed, the polymer blocks of the soft segment are regularly and spontaneously arranged in a plurality of spaces defined by the hard segment and the self-assembly of the monomers constituting the acrylamide-based monomer. Block copolymers can be formed. The regular arrangement of such soft segment polymer blocks appears to be due to microphase separation between crystalline hard segments and amorphous soft segments.

As a result, in the diblock copolymer and the polymer thin film treated with the solvent aging method or the heat treatment method, the hard segment including the repeating unit of Formula 1 or the soft segment including the repeating unit of Formula 2 may be used. For example, a nanostructure (nano pattern) in which the remaining segments are regularly arranged in a cylinder form or the like may be formed. In addition, the diblock copolymer and the polymer thin film may have a nano structure in which the cylinder form is regularly arranged in a square shape or the like by adjusting the processing conditions such as the solvent aging method or the heat treatment method. Formation of such regular nanostructures or nanopatterns can be confirmed through SEM photographs of the polymer thin film.

Meanwhile, the diblock copolymer and the respective segments thereof according to the embodiment of the present invention will be described in more detail below.

), 메타페닐렌(meta-phenylene,

), 파라페닐렌(para-phenylene,

), 나프탈렌(naphthalene,

), 아조벤젠(azobenzene,

), 안트라센(anthracene,

), 페난스렌(phenanthrene,

), 테트라센(tetracene,

), 파이렌(pyrene,

) 또는 벤조파이렌(benzopyrene,

) 등을 들 수 있다. The diblock copolymer according to the embodiment of the present invention includes a hard segment including a repeating unit of Formula 1. In the repeating unit of Formula 1, Z may be any arylene having 6 to 20 carbon atoms. Examples of such arylene include ortho-phenylene,

), Meta-phenylene,

), Para-phenylene,

), Naphthalene,

), Azobenzene (azobenzene,

), Anthracene,

), Phenanthrene

), Tetratracene,

), Pyrene,

) Or benzopyrene,

), And the like.

In addition, the R 'may be a linear or branched aliphatic hydrocarbon substituted in the ortho, meta or para position of the aromatic ring included in Z, such a hydrocarbon is 10 or more carbon atoms, more specifically 10 to 20 carbon atoms It can have a long chain length of. Further, the hydrocarbon of R 'may be substituted with fluorine, and R' may be a linear or branched perfluorohydrocarbon having 10 to 20 carbon atoms.

As the repeating unit of Formula 1 and the monomer of Formula 4 to be described later have such a long-chain hydrocarbon and arylene, the crystallinity and self-assembly characteristics of the hard segment or its monomers can be prominently displayed, and as a result fine phase separation phenomenon By the remaining segments on either of the crystalline hard segment or the amorphous soft segment may be regularly arranged in a square shape or the like to form a nanostructure or nano pattern.

The hard segment may include only one type of repeating unit belonging to Formula 1, but may include a repeating unit in the form of a copolymer, including two or more repeating units belonging to the category of Formula 1.

In addition, the diblock copolymer according to an embodiment of the present invention includes an amorphous soft segment together with the hard segment described above, and the soft segment includes a (meth) acrylate-based repeating unit of Chemical Formula 2. Such (meth) acrylate-based repeating units are conventional acrylate- or methacrylate-based monomers such as methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (ethyl acrylate; EA), ethyl methacrylate (EMA), n-butyl acrylate (BA) or n-octyl acrylate (BA). Can be. In addition, the soft segment may include only one repeating unit derived from a single acrylate-based or methacrylate-based monomer, but may be in the form of a copolymer derived from two or more acrylate-based or methacrylate-based monomers. It may also include a repeating unit, that is, two or more repeating units.

In addition, the diblock copolymer may have a number average molecular weight of about 5000 to 200000, or a number average molecular weight of about 10000 to 100000. In addition, the soft segment included in the diblock copolymer may have a number average molecular weight of about 3000 to 100000, or a number average molecular weight of about 5000 to 80000. In addition, the diblock copolymer may include about 20 to 80 mol%, or about 30 to 70 mol% of the hard segment, and about 80 to 20 mol%, or about 70 to 30 mol% of the soft segment.

As the diblock copolymer satisfies these molecular weight characteristics and the content range of each segment, the diblock copolymer is treated with a solvent aging method or a heat treatment method to obtain a polymer thin film including a regular nanostructure or nanopattern. It can be preferably formed, it can be suitably applied to the nano-pattern formation of various devices.

In addition, the hard segment having the crystallinity and the diblock copolymer including the same may have a melting point (T _m ) of about 200 to 300 ° C., or a melting point of about 220 to 280 ° C. In addition, the amorphous soft segment may have a glass transition temperature (Tg) of about 105 to 130 ° C, or a glass transition temperature of about 110 to 120 ° C. As the hard and soft segments have a melting point and a glass transition temperature range in this range, a polymer thin film including a regular nanostructure or nanopattern may be more preferably formed.

On the other hand, according to another embodiment of the invention, there is provided a method for producing the diblock copolymer described above. The method for preparing a diblock copolymer includes RAFT polymerizing a reactant including at least one (meth) acrylate monomer of Formula 3 in the presence of a radical initiator and a RAFT reagent; And RAFT polymerizing the reactant comprising at least one monomer of Formula 4 in the presence of the polymerization product:

(3)

[Formula 4]

In Formulas 3 and 4, R ₁ , R ₂ , R and R 'are as defined in Formulas 1 and 2.

Thus, RAFT polymerization of the (meth) acrylate monomer of Formula 3 to form a polymer block to form a soft segment, and in the presence of RAFT polymerization of the acrylamide monomer of Formula 4 to form a polymer block forming a hard segment Thus, the diblock copolymers of one embodiment can be readily prepared. That is, when the first RAFT polymerization step is performed, a polymer in which the RAFT reagent is coupled to both terminals thereof may be prepared while the monomer of Formula 3 is polymerized. Subsequently, when the polymer is used as a kind of macroinitiator and proceeds to RAFT polymerization of the monomer of Formula 4, the monomer of Formula 4 may be polymerized and bonded to the end of the macroinitiator. Diblock copolymers comprising hard and soft segments in one embodiment can be prepared.

 As described above, the diblock copolymer and the polymer thin film including the same may be formed on one segment of the hard segment or the soft segment due to the self-assembly and crystallinity of the hard segment polymerized with the monomer of Formula 4, and the like. The remaining segments may exhibit a regularly arranged characteristic such as a cylinder shape. Therefore, by using the diblock copolymer, a polymer thin film in which the cylinder form is regularly arranged in a square shape or the like may be manufactured, and this may be appropriately applied to forming micro patterns of various electronic devices or manufacturing nano biosensors.

Hereinafter, the method for preparing the diblock copolymer described above will be described in more detail step by step.

First, in the preparation method, any of the well-known (meth) acrylate monomers may be used as the monomer of Formula 3, and specific examples thereof include methyl acrylate (MA) and methyl methacrylate (methyl). methacrylate (MMA), ethyl acrylate (EA), ethyl methacrylate (EMA), n-butyl acrylate (BA) or n-octyl acrylate BA) etc. are mentioned, Of course, you may use 2 or more types of monomers selected from these.

In addition, any monomer satisfying the structure of Chemical Formula 4 may be used as the monomer of Chemical Formula 4, and specific examples thereof may be paradodecylphenylacrylamide [N- (p-dodecyl) phenyl acrylamide, DOPAM], paratetra. Decylphenylacrylamide [N- (p-tetradecyl) phenyl acrylamide, TEPAM], parahexadecylphenylacrylamide [N- (p-hexadecyl) phenyl acrylamide, HEPAM), paradodecylnaphthylacrylamide [N- (p -dodecyl) naphthyl acrylamide, DONAM], paratetradecylnaphthyl acrylamide [N- (p-tetradecyl) naphthyl acrylamide, TENAM], parahexadecylnaphthyl acrylamide [N- (p-hexadecyl) naphthyl acrylamide, HENAM) , Paradodecyl azobenzene nil acrylamide [N- (p-dodecyl) azobenzenyl acrylamide, DOAZAM], para tetradecyl azobenzene nil acrylamide [N- (p-tetradecyl) azobenzenyl acrylamide, TEAZAM] [N- (p-hexadecyl) azobenzenyl acrylamide, HEAZAM], or N- [4- (3- (5- ( 4-dodecyl-phenylcarbamoyl) pentyl-carbamoyl) -propyl) phenyl acrylamide {N- (4- (3- (5- (4-dodecyl-phenylcarbamoyl) pentyl-carbamoyl) -propyl) phenyl acrylamide, DOPPPAM ) And two or more kinds of monomers selected from these may be used.

In addition, the monomer of Formula 4 may take the form of the monoclinic crystal structure described above, for example, monoclinic single crystal. After the monomers are obtained in the form of monoclinic single crystals, such monomer molecules may be more regularly aligned and well-oriented monomer molecules may be combined by forming hard segments and diblock copolymers through RAFT polymerization or the like. As a result, more regular spaces are defined on these hard segments, and soft segments are regularly arranged within the spaces, thereby producing a diblock copolymer having a better and regular nanostructure and nanopattern, and a polymer thin film. Can be.

In order to obtain the monomer of Formula 4 in the form of a single crystal, a single crystal may be grown by adding a crystal growth agent in a polar solvent and / or a nonpolar solvent after the monomer synthesis. In this case, the growth rate of the single crystal may be determined depending on the composition and ratio of the polar solvent and the nonpolar solvent used, the crystal growth time and temperature, the chemical structure and the concentration of the added crystal growth agent, and the like.

On the other hand, in the production method of the other embodiment, first, in the presence of a radical initiator and a RAFT reagent, RAFT polymerization of a reactant comprising at least one (meth) acrylate monomer of the formula (3). As a result, a kind of macroinitiator of the form in which the RAFT reagent is bonded to both ends of the (meth) acrylate polymer polymerized with the monomer of Formula 3 may be obtained.

In this case, the radical initiator, the RAFT reagent and the monomer of Formula 3 may be prepared as a reaction solution dissolved in an organic solvent, and the RAFT polymerization process may be performed in the reaction solution state. In this case, the organic solvent is one or more halogen- or aromatic solvents selected from the group consisting of methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran (THF), dioxane, monoglyme, diglyme, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), and the like. Or two or more polar mixed solvents can be used. Such an organic solvent may be used in about 2 to 10 times the weight of the monomer of formula (3). This organic solvent may be used as a reaction medium in the RAFT polymerization step for the monomer of Formula 4 described below.

As the radical initiator, any initiator known to be usable for radical polymerization may be used without any particular limitation. Examples of such radical initiators include azobisisobutyronitrile (AIBN), 2,2'-azobis-2,4-dimethylvaleronitrile (2,2'-azobis- (2,4-dimethylvaleronitrile), Benzoyl peroxide (BPO) or di-t-butyl peroxide (DTBP), and the like, and two or more selected from them may be used. It may likewise be used in the RAFT polymerization step for the monomer of 4.

Moreover, as said RAFT reagent, S-1-dodecyl-S '-((alpha,)'-dimethyl- alpha'-acetic acid) trithiocarbonate [S-1-dodecyl-S '-((alpha, alpha') -dimethyl-α-acetic acid trithiocarbonate], cyanoisopropyl dithiobenzoate, cumyl thiobenzoate, cumyl phenylthioacetate, 1-phenylethyl-1 -Phenyldithioacetate (1-phenylethyl-1-phenyldithioacetate), or 4-cyano-4- (thiobenzoylthio) -N-succinimidebarrate (4-cyano-4- (thiobenzoylthio) -N-succinimide pyrolysis initiators such as valerate), and mixtures of two or more selected from them may be used.

The RAFT reagent may be used in a ratio of about 0.001 to 5.0 mol% based on the weight of the monomer of Formula 3, and the radical initiator may be used in a molar equivalent ratio of about 0.1 to 1.0 with respect to the RAFT reagent. With this content, the RAFT polymerization process can be effectively carried out using radical initiators and RAFT reagents.

When the RAFT polymerization process is performed on the monomer of Formula 3, a type of macroinitiator of the type in which the RAFT reagent is bonded to both ends of the (meth) acrylate polymer polymerized with the monomer of Formula 3 may be obtained. Such a macroinitiator may have a molecular weight corresponding to the soft segment molecular weight of the final diblock copolymer, and may have a number average molecular weight of about 3000 to 100000, or a number average molecular weight of about 5000 to 50000.

On the other hand, after the RAFT polymerization process of the formula (3), the RAFT polymerization step for the monomer of the formula (4) in the presence of its polymerization product, that is, the macroinitiator and radical initiator. This RAFT polymerization process can be carried out using the radical initiator and the organic solvent in the same kind and amount as in the first RAFT polymerization process, but in the presence of the above-mentioned macroinitiator in place of the RAFT reagent. As a result, a hard segment is formed while the monomer of Formula 4 is polymerized, and the diblock copolymer of one embodiment may be prepared while the hard segment is bonded to both ends of the macroinitiator. More specifically, after the RAFT polymerization process of Chemical Formula 3, the macroinitiator, the radical initiator, the monomer of Chemical Formula 4 and the organic solvent are uniformly mixed to form a solution, and after removing the oxygen present in the solution under a nitrogen atmosphere, RAFT polymerization of the monomer of Formula 4 may be performed.

In the above-described preparation method, each RAFT polymerization process for the monomers of Formulas 3 and 4 may be carried out at a reaction temperature of about 60 to 140 ℃. In addition, the RAFT polymerization process may be performed for about 30 to 200 hours, more specifically about 50 to 170 hours.

In addition, after the RAFT polymerization step for the monomer of Formula 4, the step of precipitating the polymerization product thereof in the non-solvent can be further proceeded. As a result, the diblock copolymer of one embodiment can be obtained with high purity. As the non-solvent, a solvent which does not dissolve the above-described polymerization product (eg, a polymer corresponding to each segment and a diblock copolymer of one embodiment) may be used. Examples of such nonsolvents include methanol, ethanol, normal propanol, isopropanol, or And polar solvents such as ethylene glycol, and nonpolar solvents such as normal hexane, cyclohexane, normal heptane or petroleum ether, and two or more mixed solvents selected from them may be used.

On the other hand, according to another embodiment of the invention, it is provided in a polymer thin film and a manufacturing method comprising the above-described diblock copolymer. First, the polymer thin film may include a diblock copolymer of one embodiment, and the remaining segments may be regularly arranged in a cylindrical shape or a spherical shape on any one of the hard segment or the soft segment. In addition, the method of manufacturing a polymer thin film may include applying a solution of a diblock copolymer onto a substrate to form a thin film; And subjecting the applied thin film to solvent aging in a mixed solvent of a non-polar solvent and a polar solvent, or thermally treating each of the hard segment at the melting point of the hard segment and the glass transition temperature of the soft segment.

Hereinafter, a method of manufacturing a polymer thin film and a polymer thin film manufactured using the same according to another embodiment will be described in detail.

As described above, the diblock copolymer of one embodiment may be formed on the segment of any one of the hard segment or the soft segment due to the crystallinity and self-assembly characteristics of the hard segment and the monomer for forming the same, and the fine phase separation between the segments. It may be prepared in the form of a polymer thin film including nanostructures or nano-patterns of the remaining segments arranged regularly. More specifically, after preparing a diblock copolymer according to the method of another embodiment described above, it is dissolved in an organic solvent and applied to the substrate using a spin coater or the like, and the applied thin film is solvent-aged or By the heat treatment, it was confirmed that a polymer thin film in which the remaining segments were regularly arranged in a cylinder shape or a sphere shape on one segment could be obtained.

Particularly, the cylindrical pattern arranged on the polymer thin film may be formed according to the control of solvent maturation or heat treatment conditions. On one side of the thin film), it was confirmed that it can be regularly arranged in a variety of shapes, such as lamellar, square or hexagonal shape. For example, when viewed on one side of the polymer thin film, it may be regularly arranged in a lamellar shape, or may be arranged in a square or hexagonal shape as viewed from the top or one side of the polymer thin film. By using such a polymer thin film, it is possible to selectively decompose and remove the nano pattern of the segment, for example, the soft segment, by the ultraviolet ray irradiation, and the remaining segments on the substrate, for example, hard segment The lower layer (the pattern target layer on the substrate) may be etched using the as a mask and patterned into a desired shape. In addition, since the nano-patterns arranged in a square shape, which were difficult to implement in the case of the previous block copolymer, can also be easily formed, the polymer thin film may be formed in a micro-pattern forming process of various electronic devices including next-generation semiconductor devices, or nano-bio. It can apply suitably to manufacture of a sensor.

In order to form such a polymer thin film, first, a diblock copolymer of one embodiment is dissolved in an organic solvent and coated on a substrate. In this case, the diblock copolymer may have a number average molecular weight of about 5000 to 200000, or a number average molecular weight of about 10000 to 100000. In addition, the diblock copolymer may include about 20 to 80 mol%, or about 230 to 870 mol% of the hard segment, and about 80 to 20 mol%, or about 70 to 30 mol% of the soft segment.

As the diblock copolymer satisfies these molecular weight characteristics and the content range of each segment, the diblock copolymer is treated with a solvent aging method or a heat treatment method to obtain a polymer thin film including a regular nanostructure or nanopattern. It can form preferably.

In addition, the organic solvent is n-hexane, n-heptane, n-octane, cyclohexane, methylene chloride, 1,2-dichloroethane, chloroform, ethyl ether, benzene, chlorobenzene, dichlorobenzene, toluene, THF, acetone One or more solvents selected from nonpolar or polar solvents such as dioxane, methanol, ethanol, ethyl acetate, DMF, DMAC, or DMSO can be used. The amount of the organic solvent is suitably at least about 10 times the weight of the diblock copolymer.

In order to apply the organic solution of the diblock copolymer to a uniform thickness, the organic solution may be spin-coated on a substrate with a spin coater or the like to form a thin film. At this time, the number and concentration of the solvent, as well as the rotational speed and rotational time of the spin coater is important, in consideration of this point the rotational speed and time can be adjusted between about 2000-4000 rpm, about 20-60 seconds respectively.

On the other hand, after applying the solution of the diblock copolymer, the step of solvent aging or heat treatment of the thin film is carried out. In this case, in the solvent aging method, the same organic solvent as that used for the dissolution of the diblock copolymer may be used, but it is preferable to use two or more mixed solvents each selected from a nonpolar solvent and a polar solvent. In addition, the solvent aging may proceed for about 4 to 96 hours at room temperature. In the heat treatment method, the heat treatment is performed for about 2 to 24 hours at the melting point (T _m ) of the repeating unit of Formula 1 forming the hard segment and the glass transition temperature (T _g ) of the repeating unit of the Formula 2 forming the soft segment. can do. Under the above-described conditions, as the solvent aging or heat treatment proceeds, a more regular soft segment nanostructure or nanopattern may be formed on the polymer thin film.

In addition, by adjusting the solvent aging or heat treatment conditions, the arrangement of the nano-pattern having the cylindrical form or the like can be adjusted to various shapes such as lamellar, square or hexagonal. In addition, in order to uniformly arrange the nanopattern in a desired shape, the molecular weight of the diblock copolymer or the chemical structure or composition ratio of each segment may also be appropriately adjusted.

On the other hand, according to another embodiment of the invention, there is provided a nano-pattern forming method using the above-described polymer thin film. The nano-pattern forming method may include forming a polymer thin film on the substrate on which the pattern target film is formed by the above-described method; Selectively removing any one segment arranged in the form of a cylinder or a sphere from the polymer thin film; And reactive ion etching the pattern target layer using the polymer thin film having any one segment removed thereon as a mask. One embodiment of such a nano-pattern forming method may include forming a polymer thin film on the substrate on which the pattern target film is formed by the above-described method; Irradiating ultraviolet light to the polymer thin film to remove the soft segment; And reactive ion etching the pattern target layer using the polymer thin film from which the soft segment has been removed as a mask.

Through this method, it is possible to easily fine-pattern the pattern target film on the substrate according to the nano-pattern formed on the polymer thin film without using a metal mold aid such as a separate photomask.

In the nano-pattern forming method, first, the polymer thin film may be irradiated with ultraviolet rays to decompose any one segment, for example, a soft segment, arranged in the form of a cylinder or a sphere, and then solvent treatment or acid treatment may be performed. The disassembled segment can be removed via Such as this ultraviolet ray irradiation, for example, acetic acid (trifluoroacetic acid) with ultraviolet rays of 254 nm wavelength in an area (cm ²⁾ may proceed in a manner that irradiation by about 5 to 50 joules (Joule) sugars, acetic acid or trifluoroacetic The acid can be treated to remove the UV decomposed segment.

When any one of the segments is removed, only the remaining segments, for example, hard segments, remain in the polymer thin film, so that the pattern target layer on the substrate may be exposed in a portion where the nano pattern of the segment is formed in a cylinder shape or the like. Thus, when the polymer thin film is used as a mask and the reactive ion etching of the pattern target layer is performed, the pattern target layer may be selectively etched and removed only in the exposed portion, thereby patterning the pattern target layer in a desired pattern form.

This reactive ion etching step may be performed by etching under general conditions (for example, 40/20 SCCM, 80 Watt, 1-10 minutes) of CF ₄ / Ar gas ions, wherein the patterned film is formed of silicon. It may be a thin film containing.

Meanwhile, after the reactive ion etching step, the step of removing the polymer thin film by treatment with oxygen plasma may be further performed to remove the polymer thin film (eg, hard segment) remaining on the patterned pattern target layer. Such oxygen plasma can be prepared under conventional conditions, eg, about 40 sccm; About 50 W; Treatment may be performed under a condition of about 1-10 minutes. As a result, cylindrical nano-patterns arranged in a lamellar, square or hexagonal shape may be transferred to a pattern target film including silicon or the like to form a desired nanostructure. .

As described above, the present invention provides a novel diblock copolymer comprising an acrylamide-based hard segment and a (meth) acrylate-based soft segment, a polymer thin film including the same, and a method of manufacturing the same. Such a diblock copolymer and a polymer thin film can easily form a nanostructure or nanopattern on which one segment is regularly arranged in the form of a cylinder or the like.

In particular, only by controlling the polymer morphology by adjusting the formation conditions (eg, solvent maturation conditions or heat treatment conditions) of the polymer thin film, the nano-pattern such as the cylindrical shape is lamellar, square or hexagonal It is possible to form nanostructures arranged in a variety of desired shapes, such as, in particular, it is possible to easily form a cylindrical nano-pattern arranged in a square shape that was difficult to form before.

Accordingly, the soft segment is selectively removed from the polymer thin film by ultraviolet rays, and the pattern thin film is reactively etched using the polymer thin film as a mask. Can be.

Therefore, by using the polymer thin film or the like, a very fine pattern can be easily formed than that formed in the previous photolithography, and in particular, a square-shaped array pattern, which is difficult to form even with other block copolymers or the like, is relatively easy to form. Can be formed. As a result, it has been confirmed that such a diblock copolymer, a polymer thin film, and the like can be suitably applied to a fine pattern forming process of various electronic devices including next-generation semiconductor devices, manufacturing of nano biosensors, and the like.

FIG. 1A is a SEM photograph of the surface and the cross section of the nanostructure on the polymer thin film formed in Example 12. FIG.
FIG. 1B is an enlarged photograph of a nanostructure on a polymer thin film formed in Example 12 and measured by SEM. FIG.
Figure 2a is a photograph of the nanostructure of the surface of the polymer thin film formed in Example 13 measured by AFM.
2b is a SEM photograph of the surface and the cross-section of the nanostructure on the polymer thin film formed in Example 13;
Figure 3a is a photograph of the nanostructure of the surface of the polymer thin film formed in Example 14 measured by AFM.
3b is a SEM photograph of the surface of the nanostructure on the polymer thin film formed in Example 14. FIG.
4A is a photograph taken by AFM of a nanostructure of the surface of the polymer thin film formed in Example 15.
Figure 4b is a photograph of the surface of the nanostructures by SEM after irradiating ultraviolet light to the polymer thin film in Example 15.
4C is a photograph taken by SEM of the surface of the nanostructure after RIE etching and oxygen plasma treatment in Example 15.
5A is a photograph taken by AFM of a nanostructure of the surface of the polymer thin film formed in Example 16.
FIG. 5B is a photograph of the surface of the nanostructure measured by AFM after ultraviolet irradiation to the polymer thin film in Example 16. FIG.
5C is a photograph taken by SEM of the surface of the nanostructure after RIE etching and oxygen plasma treatment in Example 16.
6A is a photograph taken by AFM of the nanostructure of the surface of the polymer thin film formed in Example 17.
FIG. 6B is a photograph taken by SEM after irradiating UV light to a polymer thin film in Example 17. FIG.
7A is a photograph taken by AFM of a nanostructure of the surface of a polymer thin film formed in Example 18. FIG.
FIG. 7B is a photograph taken by SEM after irradiating UV light to a polymer thin film in Example 18. FIG.

Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific examples of the invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

Examples 1 and 2: Synthesis and Crystallization of Acrylamide-Based Monomers

Example 1 Synthesis of Paradodecylphenylacrylamide (DOPAM) and Preparation of Single Crystal

First, paradodecylaniline (12 g, 0.046 mol) is dissolved in 100 mL of THF as a solvent, and then put into a 100 mL 3-necked round flask, and the same molar ratio of imidazole and triethyl amine (0.023 mol) is obtained. Drop the mixed acid remover through a funnel for 10 minutes, and then add a solution of acrylloyl chloride (3.8 mL, 0.047 mol) in 20 mL of THF to this mixed solution under a nitrogen atmosphere. Dropped slowly for 20 minutes. At this time, the reaction mixture was cooled with ice so that the temperature of the reaction mixture did not rise above 5 ° C. Thereafter, the reaction was carried out at 0 ° C. for 6 hours, and then at 25 ° C. for 9 hours. After the reaction was terminated, the solution was filtered through a filter paper to remove salt precipitate, and then the solvent was removed using an evaporator. The obtained solid was dissolved in 100 mL of dichloromethane, poured into a separatory funnel with a 50 mL aqueous solution of 10% NaHCO ₃ , shaken vigorously, and the aqueous layer was separated to remove unreacted acryloyl chloride. Magnesium sulfate (1.0 g) was added to the separated dichloromethane solution, stirred for 5 hours, and filtered to remove the trace amount of water dissolved in the solvent. The dichloromethane solution thus obtained was evaporated. Then, 100 mL of n-hexane was added, stirred for 2 hours, and filtered to remove unreacted paradodecylaniline remaining in the solution. The solvent was removed from the remaining solution using an evaporator to give a white solid DOPAM (yield 95%; melting point: 101 ° C.). The chemical structure of the synthesized DOPAM was confirmed by the hydrogen nuclear magnetic resonance ( ¹ H-NMR) spectrum, the results are as follows.

¹ H-NMR (CDCl ₃ ): e, δ 7.5 (d, 2H); d, δ 7.2 (s, 1H); f, δ 7.15 (d, 2H); b, δ 6.4 (d, 1 H); c, δ 6.2 (q, 1H); b, δ 5.8 (d, 1 H); g, δ 2.6 (t, 2H); h, δ 1.25-1.35 (m, 20H); i, δ 0.935 (t, 3H).

In addition, the synthesized DOPAM (T _m = 101 ° C) was purified by recrystallization three times again with ethanol. Purified pure DOPAM was added to THF solvent, and then a few drops of nonpolar solvent were added and the monocrystals of the monomers were grown while being kept at -10 ° C or lower for a period of time. At this time, it was confirmed that the growth rate of the single crystal depends on the composition and ratio of the polar solvent and the nonpolar solvent used, the crystal growth time and temperature, the chemical structure and the concentration of the added crystal growth agent, and the like.

The crystal structure of the single crystal obtained in Example 1 was investigated using X-ray diffractometry (XRD) analysis, and the crystallographic data of the single crystal shown in Table 1 below were derived. Based on these crystallographic data, it was confirmed that the single crystal of the monomer of Example 1 exhibits a monoclinic crystal structure.

[ Example  2]: Paratetradecylphenylacrylamide ( TEPAM ) And parahexadecylphenylacrylamide ( HEPAM)  Synthesis and Preparation of Single Crystals

The same method as in Example 1 was used except that paratedecylaniline having 14 carbons or parahexadecylaniline having 16 carbons was used instead of paradodecylaniline having 12 carbons of hydrocarbons used in Example 1. TEPAM and HEPAM were synthesized, and the yields were 90% and 93%, respectively. In addition, it was confirmed that the single crystals of TEPAM and HEPAM were grown in the same manner as in Example 1 to show the monoclinic crystal structure by XRD analysis.

Examples 3 to 11: Preparation of Diblock Copolymers

Example 3 Preparation of Macroinitiator (Macro-PMMA) -1

6.0 g of monomer MMA, 66.3 mg of cyanoisopropyldithiobenzoate, RAFT reagent, 24.6 mg of radical initiator AIBN, 6.82 mL of benzene were placed in a 20 mL glass ampoule and present in solution by freeze-thawing method. After the oxygen was removed, the ampoule was sealed and subjected to RAFT polymerization for 24 hours in an oil container at 60 ° C. After polymerization, the reaction solution was immersed in 200 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a pink macroinitiator (Macro-PMMA) -1 having a RAFT reagent bonded to both ends of the polymer (PMMA) of MMA. . The polymerization conversion, number average molecular weight (M _n ), molecular weight distribution (M _w / M _n ) and glass transition temperature (T _g ) were 90%, 18400, 1.11 and 117 ^° C., respectively.

Example 4 Preparation of New Diblock Copolymer-1

0.781 g of acrylamide monomer DOPAM synthesized in Example 1, 0.450 g of Macroinitiator-1 prepared in Example 2, 4.0 mg of BPO, and 4.05 mL of benzene were added to a 10 mL Schlenk flask and stirred at room temperature under a nitrogen atmosphere for 30 minutes. After the RAFT polymerization was performed for 72 hours in a silicon oil container at 80 ℃. The polymerization solution was immersed in 200 mL of methanol and then dried to prepare a new light yellow diblock copolymer-1. Polymerization conversion, number average molecular weight, molecular weight distribution, T _g and melting temperature (T _m ) were 40%, 30900, 1.23, 119 ^o C and 233 ^o C, respectively.

Example 5 Preparation of New Diblock Copolymer-2

The process was carried out in the same manner as in Example 4 except that 0.621 g of DOPAM, 0.3 g of Macroinitiator-1, 1.82 mg of AIBN, and 3.22 mL of benzene were used to perform a RAFT polymerization reaction at a polymerization temperature of 70 ° C. for 72 hours. New yellow diblock copolymer-2 was prepared. Polymerization conversion, number average molecular weight, molecular weight distribution, T _g and T _m were 58%, 40400, 1.25, 119 ^o C and 236 ^o C, respectively.

Example 6 Preparation of New Diblock Copolymer-3

A light yellow novel diblock copolymer-3 was prepared in the same manner as in Example 5, except that 0.841 g of DOPAM, 1.84 mg of AIBN, and 4.36 mL of benzene were used. Polymerization conversion, number average molecular weight, molecular weight distribution, T _g and T _m were 57%, 46700, 1.25, 119 ^o C and 235 ^o C, respectively.

Example 7 Preparation of Macro-PMMA-2

A pink macroinitiator-2 was prepared in the same manner as in Example 3, except that the polymerization time was performed for 30 hours. The polymerization conversion, number average molecular weight, molecular weight distribution and T _g were 95%, 19400, 1.11, and 119 ^° C., respectively.

Example 8 Preparation of New Diblock Copolymer-4

The process was carried out in the same manner as in Example 5, except that 0.732 g of acrylamide-based monomer DOPAM synthesized in Example 1, 0.45 g of Macroinitiator-2 prepared in Example 7, 2.54 mg of AIBN, and 3.79 mL of benzene were used. New yellow diblock copolymer-4 was prepared. Polymerization conversion, number average molecular weight, molecular weight distribution, T _g and T _m were 66%, 40400, 1.25, 119 ^o C and 234 ^o C, respectively.

Example 9 Preparation of New Diblock Copolymer-5

A new pale yellow diblock copolymer-5 was prepared in the same manner as in Example 5, except that 0.976 g of monomer DOPAM, 0.3 g of initiator II, 1.70 mg of AIBN, and 5.51 mL of benzene were used. Polymerization conversion, number average molecular weight, molecular weight distribution, T _g and T _m were 56%, 54900, 1.30, 119 ^o C and 236 ^o C, respectively.

Example 10 Preparation of New Diblock Copolymer-6

A light yellow novel diblock copolymer-6 was prepared in the same manner as in Example 9, except that 1.220 g of DOPAM and 6.32 mL of benzene were used. Polymerization conversion, number average molecular weight, molecular weight distribution, T _g and T _m were 65%, 70800, 1.30, 119 ^o C and 236 ^o C, respectively.

Example 11 Preparation of New Diblock Copolymer-7

A light yellow novel diblock copolymer-7 was prepared in the same manner as in Example 9, except that 1.216 g of TEPAM and 6.32 mL of benzene were used. Polymerization conversion, number average molecular weight, molecular weight distribution, T _g and T _m were 57%, 60700, 1.31, 119 ^o C and 230 ^o C, respectively.

The polymerization conditions, conversion rate, molecular weight, Tg, Tm, etc. for the macroinitiators and the new diblock copolymers prepared by RAFT polymerization in Examples 3 to 11 are summarized in Table 2 below:

Polymerization Conditions and Physical Properties of Macroinitiators and Diblock Copolymers of Examples 3 to 11

division Polymerization condition Polymerization Result polymerization
Temperature ( ^oC ) polymerization
time
(h) polymerization
Conversion rate
(%) Composition ratio (mol%) ¹⁾ Molecular weight ²⁾
(M _n ) Molecular Weight
Distribution T _g
( ^o C) T _m
( ^o C) Soft segment
(PMMA) Hard segment
(PDPAA) Example 3
(Giant initiator) 60 24 90 100 0 18300 1.11 117 - Example 4 80 72 40 59 41 30900 1.23 119 234 Example 5 70 72 58 45 55 40400 1.25 119 236 Example 6 70 72 57 39 61 46700 1.25 118 235 Example 7
(Giant initiator) 60 24 95 100 0 19400 1.11 119 - Example 8 70 72 66 48 52 40400 1.25 119 234 Example 9 70 72 56 35 65 54900 1.30 119 236 Example 10 70 72 65 27 73 70800 1.30 119 236 Example 11 70 72 57 32 68 60700 1.31 119 230

¹⁾ The composition ratio of soft segment and hard segment in diblock copolymer was confirmed from GPC.

²⁾ Measured by GPC using 25 ^° C. THF solution.

Examples 12 to 18: Preparation of Polymer Thin Films and Identification of Nanopattern Forms

Example 12 Preparation of Polymer Thin Film-1 by Solvent Maturation and Identification of Nanopattern Forms

Diblock copolymer-1 having 41 mol% of the hard segment prepared in Example 4 was dissolved in a chloroform solvent to prepare a 1.0 wt% solution, and then a spin coater was used on a silicon wafer substrate at a speed of 2000 rpm for 60 seconds. Coating to form a polymer thin film. The thin film was placed in a desiccator maintained in an atmosphere of a mixed solvent vapor of THF / cyclohexane 8/2 (v / v, volume ratio) and aged for 48 hours to express nanostructures on the surface of the thin film.

Thus expressed nanostructure was confirmed using AFM (atomic force microscopy). In addition, the nanostructure-expressed thin film was placed in a container containing RuO ₄ liquid for 2 to 10 minutes, and RuO ₄ was adsorbed on the thin film, and then the nanostructure expressed using a scanning electron microscope (SEM). Was measured. The SEM photographs are shown in FIGS. 1A and 1B. Figure 1a is a photograph taken by cutting the nanostructure and the surface and the cross-section together SEM, it is confirmed that the cylindrical nano-pattern on the large surface of about 4 ㎛ is well arranged in a lamellar shape. In addition, FIG. 1B is an enlarged photograph of only the SEM cross-section of FIG. 1A, in which black cylindrical nanopatterns having a diameter of about 20 nm and an interval of about 40 nm are regularly arranged in a two-dimensional square shape. It is confirmed.

Example 13 Preparation of Polymer Thin Film-2 by Solvent Maturation and Identification of Nanopattern Forms

A thin film was prepared in the same manner as in Example 12 except that the diblock copolymer-2 having a hard segment content of 55 mol% was used in Example 5, and the nanostructure was expressed on the surface of the thin film.

Thus expressed nanostructure was confirmed using AFM (atomic force microscopy). In addition, the nanostructure-expressed thin film was placed in a container containing RuO ₄ liquid for 2 to 10 minutes, and RuO ₄ was adsorbed on the thin film, and then the nanostructure expressed using a scanning electron microscope (SEM). Was measured. The measurement results are shown in FIGS. 2A and 2B. Figure 2a is a photograph of the nanostructure of the thin film surface measured by AFM, it is confirmed that the nano-pattern is well arranged in a lamellar shape. In addition, Figure 2b is a photograph taken by cutting the nanostructure and the surface and the cross-section by SEM, it is confirmed that the cylindrical nano-pattern on the large surface of about 4 ㎛ well arranged in a lamellar shape.

Example 14 Preparation of Polymer Thin Film-3 by Solvent Maturation and Identification of Nanopattern Forms

A thin film was prepared in the same manner as in Example 12 except that the diblock copolymer-3 having a hard segment content of 61 mol% was prepared in Example 6, and the nanostructure was expressed on the surface of the thin film.

Thus expressed nanostructure was confirmed using AFM (atomic force microscopy). In addition, the nanostructure-expressed thin film was placed in a container containing RuO ₄ liquid for 2 to 10 minutes, and RuO ₄ was adsorbed on the thin film, and then the nanostructure expressed using a scanning electron microscope (SEM). Was measured. The measurement results are shown in FIGS. 3A and 3B. Figure 3a is a photograph of the nanostructure of the thin film surface measured by AFM, it is confirmed that the cylindrical nano-pattern is well arranged in a hexagonal shape. 3B is a SEM photograph of the surface of the nanostructure, and it is confirmed that the cylindrical nanopatterns are well arranged in a hexagonal shape on a wide surface of about 3 μm.

Example 15 Preparation of Polymer Thin Film-4 by Solvent Maturation Method, Selective Removal of Soft Segment, Formation and Identification of Nano Pattern

Diblock copolymer-4 having a 52 mol% hard segment content in Example 8 was dissolved in a chloroform solvent to form a 1.0 wt% solution, and then, a spin coater was used on a silicon wafer substrate coated with SiO ₂ on the surface. A thin film was prepared by coating for 60 seconds at a speed of 3000 rpm. The thin film of diblock copolymer-4 thus prepared was placed in a desiccator maintained in an atmosphere of a mixed solvent vapor of THF / cyclohexane 8/2 (v / v, volume ratio) and aged for 24 hours to be nano-adhered to the surface of the thin film. The structure was expressed.

The nanostructured thin film was placed in a vial containing RuO ₄ liquid, adsorbed RuO ₄ for 2 minutes, irradiated with UV light having a wavelength of 254 nm for 15 minutes, and 20 minutes in 10 mL of 99.5% acetic acid solution. After soaking, it was taken out, washed several times with water and dried to prepare a thin film engraved with nanostructures selectively remove the soft segment of diblock copolymer-4. The thin film was etched with a RIE under normal conditions (CF ₄ / Ar = 40/20 sccm; 80 W; 120 seconds) using a mask, and finally an oxygen plasma (40 sccm; 50 W; 60 seconds) was irradiated to form SiO ₂ . A nanostructure in which nanostructures were transferred on a substrate of a coated silicon wafer was fabricated.

The nanostructures thus prepared were identified using AFM (atomic force microscopy). In addition, the nanostructures were placed in a container containing RuO ₄ liquid for 2 to 10 minutes and RuO ₄ was adsorbed onto the thin film, and the nanostructures were measured using a scanning electron microscope (SEM). The measurement results are shown in FIGS. 4A to 4C. 4A is a photograph of AFM measurement of the nanostructure of the surface of the thin film immediately after formation of the polymer thin film, confirming that the cylindrical nanopatterns are well arranged in a lamellar shape. In addition, Figure 4b is a SEM photograph of the surface of the nanostructure immediately after UV irradiation, the cylindrical nano-pattern is well arranged in a lamellar shape on a large surface of about 3 ㎛, in particular, only the soft segment is selectively removed It is confirmed that the nanopattern is formed in the form. 4C is a SEM photograph of the surface of the nanostructure after RIE etching and oxygen plasma treatment. The nanopattern having a size of about 20 nm is lamella-shaped at about 45 nm on a large silicon substrate of about 2 μm. It is confirmed that they are arranged regularly.

[Example 16] Preparation of Polymer Thin Film-5 by Solvent Maturation, Selective Removal of Soft Segments, Formation and Identification of Nanopatterns

A thin film was prepared in the same manner as in Example 12 except that the diblock copolymer-5 having a hard segment content of 65 mol% was prepared in Example 9, and the nanostructure was expressed on the surface of the thin film. The thin film was irradiated with ultraviolet rays for 20 minutes and irradiated with 50 W of RIE for 30 seconds to perform the same etching method as in Example 15, to fabricate a nanostructure to which the nanostructure was transferred.

The nanostructures thus prepared were identified using AFM (atomic force microscopy). In addition, the nanostructures were placed in a container containing RuO ₄ liquid for 2 to 10 minutes and RuO ₄ was adsorbed onto the thin film, and the nanostructures were measured using a scanning electron microscope (SEM). The measurement results are shown in FIGS. 5A to 5C. 5A is a photograph of AFM measurement of the nanostructure of the surface of the thin film immediately after the formation of the polymer thin film, confirming that the cylindrical nanopatterns are well arranged in a two-dimensional square shape. In addition, Figure 5b is an AFM photograph of the surface of the nanostructure immediately after the ultraviolet irradiation, a black cylindrical nano-pattern having a diameter of about 20nm, spaced about 45nm is well arranged in a two-dimensional square shape, In particular, it is confirmed that the nanopattern is formed in a form in which only the soft segment is selectively removed. 5C is a SEM photograph of the surface of the nanostructure after RIE etching and oxygen plasma treatment, in which a cylindrical nanopattern having a diameter of about 25 nm perpendicular to the silicon substrate is spaced about 50 nm in a square shape. It is confirmed that they are arranged regularly.

Example 17 Preparation of Polymer Thin Film-6 by Solvent Maturation, Selective Removal of Soft Segments, Formation and Identification of Nanopatterns

A thin film was manufactured in the same manner as in Example 15, except that the diblock copolymer-6 having a content of the hard segment prepared in Example 10 was 73 mol%, and the nanostructure was expressed, followed by the same ultraviolet ray as in Example 15. Only the etching process was performed to prepare a thin film engraved nanostructures.

The nanostructures thus prepared were identified using AFM (atomic force microscopy). In addition, the nanostructures were placed in a container containing RuO ₄ liquid for 2 to 10 minutes and RuO ₄ was adsorbed onto the thin film, and the nanostructures were measured using a scanning electron microscope (SEM). The measurement results are shown in FIGS. 6A and 6B. 6A is a photograph of AFM measurement of the nanostructure of the surface of the thin film immediately after the formation of the polymer thin film, confirming that the cylindrical nanopatterns are well arranged in a hexagonal shape. 6B is a SEM photograph of the surface of the nanostructure immediately after UV irradiation. A large surface of a large silicon substrate having a black cylindrical nanopattern having a diameter of about 20 nm and a spacing of about 40 nm is about 2 μm. It is confirmed that the nano-pattern is formed in a well-arranged perpendicular to, in particular, only the soft segment is selectively removed.

[Example 18] Preparation of Polymer Thin Film-7 by Solvent Maturation, Selective Removal of Soft Segments, Formation and Identification of Nanopatterns

A thin film was prepared in the same manner as in Example 16 except for using the diblock copolymer-7 having a content of 68 mol% of the hard segment prepared in Example 11, and expressing a nanostructure, followed by the same ultraviolet ray as that of Example 16. Only the etching process was performed to prepare a thin film engraved nanostructures.

The nanostructures thus prepared were identified using AFM (atomic force microscopy). In addition, the nanostructures were placed in a container containing RuO ₄ liquid for 2 to 10 minutes and RuO ₄ was adsorbed onto the thin film, and the nanostructures were measured using a scanning electron microscope (SEM). The measurement results are shown in FIGS. 7A and 7B. 7A is a photograph of AFM measurement of the nanostructure of the surface of the thin film immediately after formation of the polymer thin film, confirming that the cylindrical nanopatterns are well arranged in a hexagonal shape. FIG. 7B is a SEM photograph of the surface of the nanostructure immediately after UV irradiation. A large surface of a large silicon substrate having a diameter of about 25 nm and a black cylindrical nano pattern having a spacing of about 50 nm is about 2 μm. It is confirmed that the nano-pattern is formed in a well-arranged perpendicular to, in particular, only the soft segment is selectively removed.

Claims (23)

A hard segment including at least one repeating unit of Formula 1,
A diblock copolymer comprising a soft segment containing at least one (meth) acrylate-based repeating unit of Formula 2 below:
[Formula 1]

(2)

In Formula 1, n is an integer of 5 to 600, R is hydrogen or methyl, R 'is X,

,

,

or

X is -ZR ', Y is alkylene having 1 to 10 carbon atoms, Z is arylene having 6 to 20 carbon atoms, and R' is a linear or branched hydrocarbon having 10 to 20 carbon atoms, or 10 to 20 carbon atoms. Linear or branched perfluorohydrocarbons,
In Formula 2, m is an integer of 30 to 1000, R ₁ is hydrogen or methyl, R ₂ is alkyl having 1 to 20 carbon atoms.
The method of claim 1, wherein Z is orthophenylene (ortho-phenylene,

), Meta-phenylene,

), Para-phenylene,

), Naphthalene,

), Azobenzene (azobenzene,

), Anthracene,

), Phenanthrene

), Tetratracene,

), Pyrene,

) And benzopyrene,

A diblock copolymer which is arylene selected from the group consisting of:
According to claim 1, wherein R 'is a diblock copolymer substituted in the ortho, meta or para position of the aromatic ring included in Z,
The diblock copolymer according to claim 1, having a number average molecular weight of 5000 to 200000.
The diblock copolymer according to claim 1, wherein the soft segment has a number average molecular weight of 3000 to 100000.
The diblock copolymer according to claim 1, comprising 20 to 80 mol% of the hard segment and 80 to 20 mol% of the soft segment.
The diblock copolymer of claim 1, wherein the hard segment is crystalline and the soft segment is amorphous.
RAFT polymerizing a reactant comprising at least one (meth) acrylate monomer of Formula 3 in the presence of a radical initiator and a RAFT reagent; And
A method for preparing a diblock copolymer comprising RAFT polymerizing a reactant comprising at least one monomer of Formula 4 in the presence of the polymerization product and a radical initiator:
(3)

[Chemical Formula 4]

In Formula 3, R ₁ is hydrogen or methyl, R ₂ is alkyl having 1 to 20 carbon atoms,
In Formula 4, R is hydrogen or methyl, R 'is X,

,

,

or

X is -ZR ', Y is alkylene having 1 to 10 carbon atoms, Z is arylene having 6 to 20 carbon atoms, and R' is a linear or branched hydrocarbon having 10 to 20 carbon atoms, or 10 to 20 carbon atoms. Linear or branched perfluorohydrocarbons.
The method of claim 8, further comprising the step of precipitating the polymerization product in a non-solvent.
The method of claim 8, wherein the monomer of Formula 3 is methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), ethyl methacrylate (ethyl methacrylate) EMA), n-butyl acrylate (n-butyl acrylate; BA), and n-octyl acrylate (n-octyl acrylate; BA);
The monomer of Formula 4 is paradodecylphenylacrylamide [N- (p-dodecyl) phenyl acrylamide, DOPAM], paratetradecylphenylacrylamide [N- (p-tetradecyl) phenyl acrylamide, TEPAM], parahexadecylphenyl Acrylamide [N- (p-hexadecyl) phenyl acrylamide, HEPAM), Paradodecyl naphthyl acrylamide [N- (p-dodecyl) naphthyl acrylamide, DONAM], Paratetradecylnaphthyl acrylamide [N- (p- tetradecyl) naphthyl acrylamide, TENAM], parahexadecylnaphthylacrylamide [N- (p-hexadecyl) naphthyl acrylamide, HENAM), paradodecyl azobenzeneylacrylamide [N- (p-dodecyl) azobenzenyl acrylamide, DOAZAM], Paratetradecylazobenzeneylacrylamide [N- (p-tetradecyl) azobenzenyl acrylamide, TEAZAM], parahexadecylazobenzeneylacrylamide [N- (p-hexadecyl) azobenzenyl acrylamide, HEAZAM] and N- [4- (3- (5- (4-dodecyl-phenylcarbamoyl) pentyl-carbamoyl) -propyl) phenyl acrylamide {N- [4- (3- (5- (4-dodecyl-phenylcarbamoyl) p entyl-carbamoyl) -propyl) phenyl acrylamide, DOPPPAM) is a method for producing a diblock copolymer of at least one member selected from the group consisting of.
9. The radical initiator according to claim 8, wherein the radical initiator is azobisisobutyronitrile (AIBN), 2,2'-azobis-2,4-dimethylvaleronitrile (2,2'-azobis- (2,4). -dimethylvaleronitrile), benzoyl peroxide (benzoyl peroxide, BPO) and ditertoxy butyl peroxide (di-t-butyl peroxide, DTBP) is a method for producing a diblock copolymer of at least one member selected from the group consisting of.
The method of claim 8, wherein the RAFT reagent is S-1-dodecyl-S ′-(α, α′-dimethyl-α′-acetic acid) trithiocarbonate, cyanoisopropyl dithiobenzoate, cumyldithi. Dibenzo, at least one selected from the group consisting of obenzoate, cumylphenylthioacetate, 1-phenylethyl-1-phenyldithioacetate, and 4-cyano-4- (thiobenzoylthio) -N-succinimide varate Method for producing block copolymer.
According to claim 8, wherein the RAFT polymerization step of formula 3 or 4 is methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme A process for producing a diblock copolymer which proceeds in at least one organic solvent selected from the group consisting of diglyme, dimethylformamide, dimethylsulfoxide and dimethylacetamide.
The method of claim 8, wherein the polymerization product of the RAFT polymerization step of Chemical Formula 3 comprises a polymer in which RAFT reagent is bonded to both ends of the polymer of the (meth) acrylate monomer of Chemical Formula 3.
The preparation of the diblock copolymer according to claim 9, wherein the non-solvent comprises at least one selected from the group consisting of methanol, ethanol, normal propanol, isopropanol, ethylene glycol, normal hexane, cyclohexane, normal heptane and petroleum ether. Way.
A polymer thin film comprising the diblock copolymer of claim 1, wherein the remaining segments are regularly arranged in a cylinder or sphere on one of the hard and soft segments.
17. The polymer thin film according to claim 16, wherein the cylinder shapes are regularly arranged in a lamellar, square or hexagonal shape when viewed on any one plane of the polymer thin film.
The polymer thin film according to claim 16, which is used for the manufacture of an electronic device or a nano biosensor including a nano pattern.
Applying a solution of the diblock copolymer of claim 1 on a substrate to form a thin film; And
Solvent aging the coated thin film, or the heat treatment at the melting point of the hard segment and the glass transition temperature of the soft segment, respectively.
20. The method of claim 19, wherein the applied thin film is solvent aged for 4 to 96 hours in a mixed solvent of a non-polar solvent and a polar solvent at room temperature, or 2 to 24 at the melting point of the hard segment and the glass transition temperature of the soft segment, respectively. Method for producing a polymer thin film which is heat treated for a time.
Forming a polymer thin film on the substrate on which the pattern target film is formed by the method of claim 19;
Irradiating ultraviolet light to the polymer thin film to remove the soft segment; And
Reactive ion etching the pattern target layer using a polymer thin film from which the soft segment has been removed as a mask.
The method of claim 20, wherein the removing of the soft segment comprises irradiating the polymer thin film with ultraviolet light to decompose the soft segment and removing the soft segment by acid treatment.
The method of claim 20, further comprising removing the polymer thin film by treatment with oxygen plasma after the reactive ion etching.

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